Mouseover Images

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I have a website with digital editing tutorials and I would like to add a mouseover (before and after) effect at the top of the page so a visitor will have an idea of where the tutorial is going. I have it on a couple of pages now but the java (I think it is java) is making me nuts.

Is this do-able with XWD?

Sure thing. Why not attach the .web file that you're currently working with to provide some idea of what you're trying to accomplish.

Also - I have been messing with the mouseover video and my efforts work but how the heck does one get that really cool effect onto a webpage?

Can you describe more specifically what the "cool effect" is that you're referring to?

I tried the Export to HTML and now have a confusing little folder with lots of stuff in it but I have no idea what to do with all that 'stuff'.

That (to me) is one of the very nice things about Web Designer -- you really don't have to know a lot about the exported files. Basically, what you'll get is a series of .htm files (one for each page in your project), and a single folder that neatly packages all of the necessary elements that are required to make those pages work properly in a browser.